FR2847811A1 - FILTERING COMPOSITION CONTAINING AT LEAST ONE DIBENZOYLMETHANE DERIVATIVE AND AT LEAST ONE 3- (2-AZACYCLOALKYLIDENE) -1,3-DIHYDRO-INDOL-2-ONE DERIVATIVE, PHOTOSTABILIZATION METHOD - Google Patents

Abstract

The invention relates to a cosmetic or dermatological composition, for topical use, in particular for the photoprotection of skin and hair, characterized in that it comprises at least in a cosmetically acceptable support: (a) at least one UV filter of the dibenzoylmethane derivative type and (b) at least one 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative in an effective amount.The invention also relates to a process for improving the stability of at least one derivative of dibenzoylmethane with respect to UV radiation comprising associating with said dibenzoylmethane derivative an effective amount of a 3- (2-azacycloalkylidene) -1,3-dihydroindol-2-one derivative .

Description

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FILTERING COMPOSITION CONTAINING AT LEAST ONE DERIVATIVE
DIBENZOYLMETHANE AND AT LEAST ONE DERIVATIVE OF 3- (2-
AZACYCLOALKYLIDENE) -1,3-DIHYDRO-INDOL-2-ONE; METHOD OF
The invention relates to a cosmetic or dermatological composition, for topical use, in particular for the photoprotection of skin and hair, characterized in that it comprises at least in a cosmetically acceptable support: (b) at least one filter UV of the dibenzoylmethane derivative type; and (b) at least one 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative in an effective amount of dibenzoylmethane derivative.

It is known that the luminous radiations of wavelengths between 280 nm and 400 nm allow the browning of the human epidermis, and that the wavelength rays more particularly between 280 and 320 nm, known under the name UV -B, cause erythema and skin burns that can affect the development of natural tanning. For these reasons as well as for aesthetic reasons, there is a constant demand for means of control of this natural tan to thereby control the color of the skin; it is therefore necessary to filter this UV-B radiation.

It is also known that UV-A rays of wavelengths between 320 and 400 nm, which cause browning of the skin, are capable of inducing an alteration thereof, especially in the case of a skin sensitive or skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature cutaneous aging. They promote the triggering of the erythematous reaction or amplify this reaction in some subjects and may even be the cause of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as the preservation of the natural elasticity of the skin for example, more and more people wish to control the effect of UV-A on their skin. It is therefore desirable to also filter the UV-A radiation.

In this respect, a particularly interesting family of UV-A filters currently consists of the dibenzoylmethane derivatives, and in particular 4-tert-butyl-4'-methoxydibenzoyl methane, which in fact have a high intrinsic absorption capacity. These dibenzoylmethane derivatives, which are now products that are well known per se as active filters in UV-A, are described in particular in French patent applications FR-A-2326405 and FR-A-2440933, as well as in European Patent Application EP-A-0114607; 4-tert-butyl-4'-methoxydibenzoyl methane is also currently offered for sale under the trade name "PARSOL 1789" by the company HOFFMANN LAROCHE.

Unfortunately, it turns out that the dibenzoylmethane derivatives are relatively sensitive products to ultraviolet radiation (especially UV-A), that is to say, more precisely, that they have an unfortunate tendency to degrade more or less rapidly under the action of the latter. Thus, this substantial lack of photochemical stability of the dibenzoylmethane derivatives against the ultraviolet radiation to which they are inherently intended to be subjected, does not guarantee a constant protection during prolonged exposure to the sun, so that repeated applications at intervals of time Regular and close-ups must be performed by the user to achieve effective protection of the skin against UV rays.

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The photostabilisation of the dibenzoylmethane derivatives with respect to UV radiation is, to date, a problem which has not yet been solved in a completely satisfactory manner.

However, the Applicant has now discovered, surprisingly, that by combining the dibenzoylmethane derivatives mentioned above an effective amount of a derivative of 3- (2-azacycloalkylidene) -1,3-dihydroindol-2 -one, it was possible to substantially and remarkably improve the photochemical stability (or photostability) of these same dibenzoylmethane derivatives.

This discovery, essential, is the basis of the present invention.

Thus, according to one of the objects of the present invention, it is now proposed a new cosmetic or dermatological composition, for topical use, characterized in that it comprises at least, in a cosmetically acceptable carrier: minus a UV filter of the dibenzoylmethane derivative type and (b) at least one 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative in an effective amount.

The present invention also relates to a process for improving the stability of at least one derivative of dibenzoylmethane with respect to UV radiation comprising associating with said dibenzoylmethane derivative an effective amount of at least one derivative of 2azacycloalkylidene) -1,3-dihydro-indol-2-one.

An effective amount of a 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative for the purposes of the present invention is an amount sufficient to obtain a significant and significant improvement in the photostability of the dibenzoylmethane derivative (s) of the photoprotective cosmetic composition. This minimum amount of light stabilizing agent to be used, which may vary according to the nature of the cosmetically acceptable support selected for the composition, can be determined without any difficulty by means of a conventional photostability measurement test.

For the purposes of the present invention, the term "3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative" means any simple, oligomeric or polymeric compound having on the chain grafts containing group 3 - (2-azacycloalkylidene) -1,3-dihydro-indol-2-one.

The present invention also finally relates to the use of at least one 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative in the preparation of a cosmetic or dermatological composition comprising at least a dibenzoylmethane derivative for the purpose of improving the UV stability of said dibenzoylmethane derivative.

Other features, aspects and advantages of the present invention will appear on reading the detailed description which follows.

The 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivatives according to the invention are preferably chosen from those corresponding to the following general formula (I):

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dans laquelle : R1 et R3 sont identiques ou différents et peuvent être : - un atome d'hydrogène, - un groupe alkyle en CrC22 linéaire ou ramifié, saturé ou insaturé, éventuellement substitué par un ou plusieurs groupes A1, - un cycle de 4 à 7 atomes, saturé ou insaturé, contenant éventuellement au moins un hétéroatome parmi N, 0 et S, éventuellement accolé à un autre cycle, éventuellement substitué par un ou plusieurs groupes A1, ces cycles pouvant comporter une ou plusieurs fonctions carbonyle ou thiocarbonyle,

- un des groupes C(=NR5)R'5, C(=NR6)NR'5R"5, CORS, CSRs, COORs, CONR5R'5, CSNR5R'5, S02R5, SO2NR5R'5 avec R5, R'5 et R"5 identiques ou différents désignant l'hydrogène, un radical alkyle en C1-C22, linéaire ou ramifié ou un cycle de 4 à 7 atomes, pouvant contenir au moins un hétéroatome parmi N, 0, S, isolé ou accolé à un autre cycle, ces cycles pouvant comporter une ou plusieurs fonctions carbonyle ou thiocarbonyle, le radical alkyle ou lesdits cycles étant saturés ou non et éventuellement substitués par au moins un substituant A2.

in which: R 1 and R 3 are identical or different and can be: - a hydrogen atom, - a linear or branched, saturated or unsaturated C 1 -C 22 alkyl group, optionally substituted by one or more groups A1, - a ring of 4 to 7 atoms, saturated or unsaturated, optionally containing at least one heteroatom from N, O and S, optionally attached to another ring, optionally substituted by one or more A1 groups, these rings possibly comprising one or more carbonyl or thiocarbonyl functions,

one of the groups C (= NR5) R'5, C (= NR6) NR'5R "5, CORS, CSRs, COORs, CONR5R'5, CSNR5R'5, SO2R5, SO2NR5R'5 with R5, R'5 and R "5 identical or different designating hydrogen, a linear or branched C 1 -C 22 alkyl radical or a ring of 4 to 7 atoms, which may contain at least one heteroatom from N, O, S, isolated or attached to another cycle, these rings may include one or more carbonyl or thiocarbonyl functions, the alkyl radical or said rings being saturated or not and optionally substituted by at least one substituent A2.

CSNR5R'5, S02NR5R'5, NR5S02R'5, S02R5, NRSR'SR"5R"'S+ avec R5, R'5, R"5 et R'"5 identiques ou différents désignant l'hydrogène, un radical alkyle en C1-C22, linéaire ou ramifié ou un cycle de 4 à 7 atomes, pouvant contenir au moins un hétéroatome parmi N, 0, S, isolé ou accolé à un autre cycle, ces cycles pouvant comporter une ou plusieurs fonctions carbonyle ou thiocarbonyle, le radical alkyle ou lesdits cycles étant saturés ou non et éventuellement substitués par au moins un substituant A2 ; A1 peut être : - un halogène comme F, CI, Br, - un groupe alkyle en C1-C22 linéaire ou ramifié, saturé ou insaturé, éventuellement substitué par un ou plusieurs groupes A2,

- un des groupes CF3, CN, OR5, SR5, NRsR's, C(=NR5)R'5, C(=NR5)NR'5R"5, NR5C(=NR'5)NR"5R'"5, COR5, CSR5, COORs, CONRsR's, NR5COR'5, NR5CONR'5R"5, CSNRsR's, SO2NR5R'5, NR5SO2R'5, S02R5, SiR5R'5R"5,

SiR5(OSiR'5R"5R"'5)OSiR'5R"5R'"5, NRSR'SR"5R"'S+ avec R5, R'5, R"5 et R'"5 identiques ou R2 and R4 are identical or different and can be: - a hydrogen atom, - a linear or branched C1-C22 alkyl group, optionally saturated or unsaturated, substituted by one or more groups A1, - a cycle of 4 to 7 atoms, saturated or unsaturated, optionally containing at least one heteroatom from N, O and S, optionally substituted by one or more groups A ,, which ring may be attached to another ring or to the rings of the 3- (2-azacycloalkylidene) structure -1-3-dihydro-indol-2-one object of the invention, these rings may include one or more functions carbonyl or thiocarbonyl, this ring may also be positively charged as imidazolium, pyridinium, pyrazolium, triazolium, - a halogen like F, Cl, Br, - one of CF 3, CN, OR 5, SR 5, NR 5 R 5, C (= NR 5) R '5, C (= NR 5) NR' 5 R '' 5, NR 5 C (= NR '5) NR' 5R '''5, COR5, CSR5, COOR5, CONRsR's, NR5COR'5, NR5CONR'5R "5,

CSNR5R'5, SO2NR5R'5, NR5SO2R'5, SO2R5, NRSR'SR "5R"'S + with R5, R'5, R "5 and R'" 5 being identical or different and denoting hydrogen, an alkyl radical in C1 -C22, linear or branched or a ring of 4 to 7 atoms, which may contain at least one heteroatom from N, O, S, isolated or attached to another ring, these rings may comprise one or more functions carbonyl or thiocarbonyl, the radical alkyl or said rings being saturated or not and optionally substituted with at least one substituent A2; A1 may be: - a halogen such as F, Cl, Br, - a linear or branched, saturated or unsaturated C1-C22 alkyl group, optionally substituted with one or more A2 groups,

one of the groups CF 3, CN, OR 5, SR 5, NR 5 R 5, C (= NR 5) R '5, C (= NR 5) NR' 5 R "5, NR 5 C (= NR '5) NR" 5 R'"5, COR 5, CSR5, COORs, CONRsR's, NR5COR'5, NR5CONR'5R "5, CSNRsR's, SO2NR5R'5, NR5SO2R'5, SO2R5, SiR5R'5R" 5,

SiR5 (OSiR'5R "5R"'5)OSiR'5R"5R'" 5, NRSR'SR "5R"'S + with R5, R'5, R "5 and R""5 being identical or

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 different designating hydrogen, a linear or branched C 1 -C 22 alkyl radical or a ring of 4 to 7 atoms, which may contain at least one heteroatom from N, O, S, isolated or attached to another ring, these cycles being able to have one or more carbonyl or thiocarbonyl functions, the alkyl radical or said rings being saturated or unsaturated and optionally substituted by at least one substituent A2 - a 4 to 7 atom ring, saturated or unsaturated, optionally containing at least one heteroatom from N, 0 and S, optionally substituted by one or more groups A2, this ring being able to join another cycle or the rings of the 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one structure which is the subject of the invention, these rings may comprise one or more carbonyl or thiocarbonyl functions, this ring may also be positively charged as imidazolium, pyridinium, pyrazolium, triazolium, A2 may be: a halogen such as F, Cl, Br, an alkyl group linear or branched, saturated or unsaturated C1-C22, one of the groups CF3, CN, OR, SR, NRR ', C (= NR) R', C (= NR) NR'R ", NRC (= NR ' ) NR "R" ', COR, CSR, COOR, CONRR', NRCOR ', NRCONR'R ", CSNRR', SO2NRR ', NRS02R', SO2R, SiRR'R", SiR (OSiR'R "R" ') OSiR'R "R" ', NRR'R "R"' + with R, R ', R "and R'" identical or different designating hydrogen or a linear or branched C 1 -C 22 alkyl radical. y is 1,2,3 or 4; x is 1 to 2n + 2.

Examples of linear or branched, saturated or unsaturated C 1 -C 22 alkyl groups that may be mentioned include: methyl, isopropyl, ethyl-2-hexyl, tert-butyl, ethylene and propylene. This list is not exhaustive.

Examples of heterocycles that may be mentioned include: pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, pyridine, piperidine, pyrimidine, piperazine, pyridazine, pyrazine, triazine, morpholine, pyrrolidine, thiazolidine. This list is not exhaustive.

Examples of saturated or unsaturated carbon rings with 4.5, 6 or 7 atoms that may be mentioned include: cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or cycloheptyl. This list is not exhaustive.

The 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivatives of formula (1) according to the invention may be prepared according to a synthetic process using a lactam acetal and a 1,3-dihydro-indol-2-one derivative at room temperature in anhydrous ether according to the following reaction scheme cited in the above articles:

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Dérivé 1,3-dihydro- Fournisseur Référence CAS indol-2-one i ABCR AV18764 59-48-3 M~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ CC≥ Maybridge RH 01320 61-70-1 CC≥ MicroChemistry Ltd 39248 61-28-9 o Specs AK-830/25033062 o H Finorga SA 000048 1 0 FnorgaSA 000048 '0 N H /0:00= Maybridge SEW 04570 6286-64-2 '0 1 0 N ci Aldrich 12,748-5 17630-75-0 I II o ABCR AV9674 56341-37-8 CI N 0 Maybridge RH 01323 20870-89-7 I 0 N o I 0 MDPI 11566 )l H N 1 H N 0 i MDPI 11349 o 1 o MDPI 11349 N \ N H H 0:≥ Specs AC-907/25005257 C\/ o F F \ I o Butt Park Ltd 24/07-32 u 'N F Many lactam and 1,3-dihydroindol-2-one derivatives are available from most chemical suppliers, for example:

Derivative 1,3-dihydro- Supplier Reference CAS Indol-2-one i ABCR AV18764 59-48-3 M ~~~~~~~~~~~~~~~~~~~~~~~~~~ Maybridge RH 01320 61-70-1 CC≥ MicroChemistry Ltd. 39248 61-28-9 Specs AK-830/25033062 o H Finorga SA 000048 1 0 FnorgaSA 000048 '0 NH / 0: 00 ~~~~~~~ = Maybridge SEW 04570 6286-64-2 '0 1 0 N and Aldrich 12,748-5 17630-75-0 I II ABCR AV9674 56341-37-8 CI No 0 Maybridge RH 01323 20870-89-7 I 0 No I 0 MDPI 11566) 1 HN 1 HN 0 i MDPI 11349 o 1 o MDPI 11349 N \ NHH 0: ≥ Specs AC-907/25005257 C / o FF \ I o Butt Park Ltd 24 / 07-32 u 'NF

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Dérivé lactame Fournisseur Référence CAS ABCR AV15332 616-45-5 O H ABCR AV12260 872-50-4 o ABCR 1549765 2687-91-4 o )\ #' Salor S36,255-7 15438-71-8 \# N O oh H BASF-Misc 3772-26-7 o H Lancaster 2555-05-7 O H Xy Aldrich M7,970-0 108-27-0 O H /\ Aldrich D18,410-1 5075-92-3 0~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ OH Aldrich 47,916-0 22677-21-0 6 H~~~~~~~~~~~~~~~~~~~~~~~~~~~ OH Aldrich 47,917-9 68108-18-9 O H D ABCR AV12271 675-20-7 o N o Advan-Synth 001427 931-20-4 1) Maybridge BTBG 00104

Lactam Derivative Supplier Reference Case ABCR AV15332 616-45-5 OH ABC AV12260 872-50-4 o ABCR 1549765 2687-91-4 o) \ # 'Salor S36,255-7 15438-71-8 \ # NO oh H BASF -Misc 3772-26-7 o H Lancaster 2555-05-7 XY Aldrich M7.970-0 108-27-0 OH / \ Aldrich D18.410-1 5075-92-3 0 ~~~~~~~ Aldrich 47.916-0 22677-21-0 6H ~~~~~~~~~~~~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Aldrich 47,917-9 68108-18-9 OHD ABCR AV12271 675-20-7 o Advan- Synth 001427 931-20-4 1) Maybridge BTBG 00104

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SYS Salor S43,760-3 19365-08-3 X J 8alor S43.760-3 19365-08-3 H N ABCR AV19374 105-60-2 O H Q ABCR AV17776 2556-73-2 0 ""H N , / Acros 29704-0010 79200-56-9 H H H / Acros 29705-0010 130931-83-8 H 0 '' NH Aldrich 32,846-4 930-21-2 r\-!"'NH \=/ 1( Salor S90,675-1 17197-57-8 cdo Acros 33584-0010 34102-49-3 (Dio Maybridge JFD 02755 Cl6 Acros 33583-5000 22031-52-3 Les acétals de lactame peuvent être obtenus à partir des lactames selon le schéma réactionnel suivant cité dans les articles Tetrahedron Letters (1994), 35 (18), 2951 - 2954 et Journal of Organic Chemistry (1984), 49,3659 - 3660 :

Selon le lactame de départ, des étapes de protection puis de déprotection de certains groupes fonctionnels comme OH ou NH, bien connues de l'homme de l'art, peuvent être nécessaires.

SYS Salor S43,760-3 19365-08-3 XJ 8alor S43.760-3 19365-08-3 HN ABCR AV19374 105-60-2 OHQ ABCR AV17776 2556-73-2 0 "" HN / Acros 29704-0010 79200-56-9 HHH / Acros 29705-0010 130931-83-8 H 0 '' NH Aldrich 32,846-4,930-21-2 (NH) = 1 (Salor S90,675-1 17197- 57-8 cdo Acros 33584-0010 34102-49-3 (Dio Maybridge JFD 02755 Cl6 Acros 33583-5000 22031-52-3 The lactam acetals can be obtained from the lactams according to the following reaction scheme cited in the articles Tetrahedron Letters (1994), 35 (18), 2951-2954 and Journal of Organic Chemistry (1984), 49, 369-3660:

Depending on the starting lactam, steps of protection and deprotection of certain functional groups such as OH or NH, well known to those skilled in the art, may be necessary.

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dans lesquelles : R1 et R3, identiques ou différents, désignent l'hydrogène, un radical alkyle en C1-C8, linéaire ou ramifié, saturé ou insaturé, le groupe phényle ou un radical COR5 ou S02R5 avec R5 désignant un radical alkyle en Ci-Ce linéaire ou ramifié, saturé ou insaturé, ou le groupe phényle ; R2 désigne l'hydrogène ; un radical alkyle en Ci-Ce, linéaire ou ramifié, saturé ou insaturé ; le groupe phényle ; un des radicaux OR5, NRsR's, NRsCOR's, COOR5 et CONR5R'5 avec R5 et R'5, identiques ou différents, désignant l'hydrogène, un radical alkyle en C1-C8 linéaire ou ramifié, saturé ou insaturé, ou le groupe phényle ; le radical CF3 ; R4 désigne l'hydrogène, un radical alkyle en C1-C8, linéaire ou ramifié, saturé ou insaturé, le groupe phényle ou un radical OR5 avec R5 désignant l'hydrogène, un radical alkyle en Ci-Ce linéaire ou ramifié, saturé ou insaturé, ou le groupe phényle ; x, y et z valent 1,2, 3 ou 4. Among the compounds of formula (I) that are preferred, mention may be made of those of formula (II) or (III) below:

in which: R1 and R3, which may be identical or different, denote hydrogen, a linear or branched, saturated or unsaturated C1-C8 alkyl radical, the phenyl group or a COR5 or SO2R5 radical with R5 denoting a C1-C8 alkyl radical; This linear or branched, saturated or unsaturated, or phenyl group; R2 is hydrogen; a linear or branched, saturated or unsaturated C 1 -C 6 alkyl radical; phenyl group; one of the radicals OR5, NRsR's, NRsCOR's, COOR5 and CONR5R'5 with R5 and R'5, which may be identical or different, denoting hydrogen, a linear or branched, saturated or unsaturated C1-C8 alkyl radical, or the phenyl group; the CF3 radical; R4 denotes hydrogen, a linear or branched, saturated or unsaturated C1-C8 alkyl radical, phenyl group or an OR5 radical with R5 denoting hydrogen, a linear or branched C1-C6 alkyl radical, saturated or unsaturated, , or the phenyl group; x, y and z are 1,2, 3 or 4.

Among the 3- (2-azacycloalkylidene) -1,3-dihydroindol-2-one derivatives of formula (I), mention will be made even more particularly of those of formula (II) in which: R2 denotes hydrogen, OR5, NRsCOR's or NR5R'5 with R5 and R'5, identical or different, denoting hydrogen, a linear or branched, saturated or unsaturated C1-C8 alkyl radical, or the phenyl group; R4 is hydrogen; R1 and R3, identical or different, denote hydrogen, a linear or branched, saturated or unsaturated C 1 -C 8 alkyl radical, or the phenyl group and even more particularly those described in the following table, commercially available from Specs / Biospecs :

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v Composé N Formule Nom (référence Specs/Biospecs) 1-Ethyl-3-(1-methyl-pyrrolidinV"" \ 2-ylidene)-1,3-dihydro-indol-2- 1 fi iJl I A= one -N (AH-262/33341016) NH 1-Ethyl-3-pyrrolidin-2-ylidene- 1,3-dihydro-indol-2-one 2 o (AH-262/33341015) N NH 3-Pyrrolidin-2-ylidene-1,3dihydro-indol-2-one [ 0 (AH-262/33341017) ~~~~ H ~~~~ ~~~~~~~~~~~~~~ Les dérivés de 3-(2-azacycloalkylidene)-1,3-dihydro-indol-2-one conformes à l'invention sont présents de préférence dans la composition de l'invention dans des proportions allant de 0,01 % à 20% en poids, et plus préférentiellement de 0,1 à 10% en poids par rapport au poids total de la composition.

v Compound N Formula Name (Specs / Biospecs reference) 1-Ethyl-3- (1-methyl-pyrrolidinyl-2-ylidene) -1,3-dihydro-indol-2-1 AH-262/33341016) NH 1-Ethyl-3-pyrrolidin-2-ylidene-1,3-dihydro-indol-2-one 2 (AH-262/33341015) N NH 3 -Pyrrolidin-2-ylidene-1 , 3dihydroindol-2-one [0 (AH-262/33341017) ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ -1,3-dihydro-indol-2-one according to the invention are preferably present in the composition of the invention in proportions ranging from 0.01% to 20% by weight, and more preferably from 0.1 at 10% by weight relative to the total weight of the composition.

As indicated above, the derivatives of dibenzoylmethane intended to be photostabilized in the context of the present invention are products already well known per se and described in particular in the documents FR2326405, FR2440933 and EP0114607 cited above, documents whose teachings are, as far as to the very definition of these products, totally included as references in the present description.

According to the present invention, it is of course possible to use one or more derivatives of dibenzoylmethane.

- le 2-méthyl-5-tert.-butyl-4'-méthoxydibenzoylméthane - le 2,4-diméthyl-4'-méthoxydibenzoylméthane - le 2,6-diméthyl-4-tert.-butyl-4'-méthoxydibenzoylméthane Among the derivatives of dibenzoylmethane falling particularly well within the scope of the present invention, mention may be made in particular, without limitation: 2-methyldibenzoylmethane - 4-methyldibenzoylmethane - 4-isopropyldibenzoylmethane - 4-tert.-butyldibenzoylmethane - 2,4-dimethyldibenzoylmethane - 2,5-dimethyldibenzoylmethane - 4,4'-diisopropyldibenzoylmethane - 4,4'-dimethoxydibenzoylmethane - 4-tert-butyl-4'-methoxydibenzoylmethane - 2-methyl-5- isopropyl-4'-methoxydibenzoylmethane

2-methyl-5-tert.-butyl-4'-methoxydibenzoylmethane - 2,4-dimethyl-4'-methoxydibenzoylmethane - 2,6-dimethyl-4-tert.-butyl-4'-methoxydibenzoylmethane

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Un autre dérivé du dibenzoylméthane préféré selon la présente invention est le 4isopropyl-dibenzoylméthane, filtre vendu sous la dénomination de "EUSOLEX 8020" par la Société MERCK, et répondant à la formule développée suivante (ou à une de ses formes tautomères) :

Le ou les dérivés du dibenzoylméthane peuvent être présents dans les compositions conformes à l'invention à des teneurs qui varient de préférence de 0,01 % à 20 % en poids, et plus préférentiellement de 0,1 à 10% en poids par rapport au poids total de la composition. Among the dibenzoylmethane derivatives mentioned above, it is particularly preferred according to the present invention to use 4- (terbutyl) -4'-methoxydibenzoylmethane, especially that sold for sale under the trade name "PARSOL 1789 by the company HOFFMANN LAROCHE, this filter thus responding to the following structural formula (or to one of its tautomeric forms):

Another preferred dibenzoylmethane derivative according to the present invention is 4isopropyl-dibenzoylmethane, a filter sold under the name "Eusolex 8020" by the company Merck, and having the following structural formula (or one of its tautomeric forms):

The derivative (s) of dibenzoylmethane may be present in the compositions in accordance with the invention at contents which preferably vary from 0.01% to 20% by weight, and more preferably from 0.1% to 10% by weight relative to total weight of the composition.

The compositions in accordance with the invention may comprise, in addition, other additional organic UV or inorganic UV screening agents active in water-soluble or fat-soluble UVA and / or UVB or insoluble in the cosmetic solvents commonly used.

The complementary organic screening agents are chosen in particular from anthranilates; cinnamic derivatives; dibenzoylmethane derivatives; salicylic derivatives, camphor derivatives; triazine derivatives such as those described in patent applications US 4367390, EP863145, EP517104, EP570838, EP796851, EP775698, EP878469, EP933376, EP507691, EP507692, EP790243, EP944624; benzophenone derivatives; ss, ss-diphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives as described in patents EP669323 and US 2,463,264; p-aminobenzoic acid derivatives (PABA); methylene bis (hydroxyphenyl benzotriazole) derivatives as described in US5,237,071, US 5,166,355, GB2303549, DE 197 26 184 and EP893119; filter polymers and silicone filters such as those described in particular in the application WO-93/04665; alkyl-styrene-derived dimers such as those described in patent application DE19855649; 4,4diarylbutadienes as described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981 and mixtures thereof.

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As examples of additional organic screening agents, mention may be made of those designated below under their INCI name: Derivatives of para-aminobenzoic acid: PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name ESCALOL 507 by ISP, Glyceryl PABA, PEG-25 PABA sold under the name UVINUL P25 by BASF, Salicylic derivatives: Homosalate sold under the name Eusolex HMS by Rona / EM Industries, Ethylhexyl Salicylate sold under the name NEO HELIOPAN OS by Haarmann and REIMER, Dipropylene glycol salicylate sold under the name DIPSAL name by SCHER, TEA Salicylate, sold under the name NEO HELIOPAN TS by Haarmann and REIMER, Derivatives of dibenzoylmethane: Butyl Methoxydibenzoylmethane sold in particular under the trade name PARSOL 1789 by HOFFMANN LA ROCHE, Isopropyl Dibenzoylmethane, cinnamic derivatives: Ethylhexyl methoxycinnamate sold in particular under the trade name PARSOL MCX by HOFFMANN LA ROCHE, Isopropyl Methoxy cinnama Isoamyl Methoxy cinnamate sold under the trade name NEO HELIOPAN E 1000 by HAARMANN and REIMER, Cinoxate, DEA Methoxycinnamate, Diisopropyl Methylcinnamate, Glyceryl Ethylhexanoate Dimethoxycinnamate Derivatives of ss, ss'-diphenylacrylate: Octocrylene sold in particular under the trade name UVINUL N539 by BASF, Etocrylene, sold in particular under the trade name UVINUL N35 by BASF, Derivatives of benzophenone: Benzophenone-1 sold under the trade name UVINUL 400 by BASF, Benzophenone-2 sold under the trade name UVINUL D50 by BASF Benzophenone-3 or Oxybenzone sold under the trade name UVINUL M40 by BASF, Benzophenone-4 sold under the trade name UVINUL MS40 by BASF, Benzophenone-5 Benzophenone-6 sold under the trade name Helisorb 11 by Norquay Benzophenone-8 sold under the trade name Spectra-Sorb UV-24 by American Cyanamid Benzophenone-9 sold under the trade name UVINUL DS-49 by BASF, Benzophenone-12 2- (4-diethyl) n-hexyl amino-2-hydroxybenzoyl) benzoate.

<Desc / Clms Page number 12>

Derivatives of benzylidene camphor: 3-Benzylidene camphor manufactured under the name MEXORYL SD by CHIMEX, 4-Methylbenzylidene camphor sold under the name EUSOLEX 6300 by MERCK, Benzylidene Camphor Sulfonic Acid manufactured under the name MEXORYL SL by CHIMEX, Camphor Benzalkonium Methosulfate manufactured under the name MEXORYL SO name by CHIMEX, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name MEXORYL SX by CHIMEX, Polyacrylamidomethyl Benzylidene Camphor manufactured under the name MEXORYL SW by CHIMEX, Derivatives duphenyl benzimidazole: Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name EUSOLEX 232 by MERCK, Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name NEO HELIOPAN AP by Haarmann and Reimer, triazine derivatives: Anisotriazine sold under the trade name Tinosorb S by Ciba Geigy, Ethylhexyl triazone sold in particular under the trade name UVINUL T150 by BASF, 2 , 4,6-tris- (4'-amino ben diisobutyl zalmalonate) -s-triazine, diethylhexyl butamido triazone sold under the trade name UVASORB HEB by SIGMA 3V, Derivatives of phenyl benzotriazole: Drometrizole Trisiloxane sold under the name Silatrizole by Rhodia Chimie, methylene bis-benzotriazolyl tetramethylbutylphenol, sold in solid form as the trade name MIXXIM BB / 100 by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion under the trade name TINOSORB M by CIBA SPECIALTY CHEMICALS, anthranilic derivatives: Menthyl anthranilate sold under the trade name NEO HELIOPAN MA by Haarmann and REIMER, Derivatives of imidazolines: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate, Derivatives of benzalmalonate: Polyorganosiloxane with benzalmalonate functions sold under the trade name PARSOL SLX by HOFFMANN LA ROCHE

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 4,4-Diarylbutadiene derivatives: -1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene and mixtures thereof.

The preferred complementary organic UV screening agents are chosen from: - Ethylhexyl salicylate, - Ethylhexyl methoxycinnamate - Octocrylene, - Phenylbenzimidazole Sulfonic Acid, - Benzophenone-3, - Benzophenone-4, - Benzophenone-5, - 2- (4-diethylamino-2- hydroxybenzoyl) -benzoate benzoate.

4-Methylbenzylidene camphor, - Terephthalylidene Dicamphor Sulfonic Acid, - Disodium Phenyl Dibenzimidazole Tetrasulfonate, 2,4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine - Anisotriazine, - Ethylhexyl triazone, - Diethylhexyl Butamido Triazone, - Methylene bis-Benzotriazolyl Tetramethylbutylphenol - Drometrizole Trisiloxane -1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene and mixtures thereof.

The inorganic complementary filters are chosen from pigments or even nanopigments (average size of the primary particles: between 5 nm and 100 nm, preferably between 10 nm and 50 nm) of coated or uncoated metal oxides, such as, for example, nanopigments. titanium oxide (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium which are all UV photoprotective agents well known per se. Conventional coating agents are, moreover, alumina and / or aluminum stearate. Such nanopigments of metal oxides, coated or uncoated, are in particular described in patent applications EP518772 and EP518773.

The complementary UV filters according to the invention are generally present in the compositions according to the invention in proportions ranging from 0.1 to 20% by weight relative to the total weight of the composition, and preferably ranging from 0.2 to 15% by weight relative to the total weight of the composition.

The cosmetic compositions according to the invention may also contain agents for tanning and / or artificial browning of the skin (self-tanning agents) such as dihydroxyacetone (DHA).

The compositions in accordance with the present invention may furthermore comprise conventional cosmetic adjuvants, chosen especially from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, humectants, antioxidants, moisturizers, desquamants, agents and the like. antiradicals, antipollution agents, antibacterials, anti-inflammatory agents, depigmenting agents, pro-pigmentants, opacifiers, stabilizers, emollients, silicones, anti-foam agents, insect repellents, perfumes , preservatives, anionic, cationic, nonionic surfactants,

<Desc / Clms Page number 14>

 zwitterionic or amphoteric, substance P antagonists, CGRP substance antagonists, fillers, pigments, polymers, propellants, alkalinizing or acidifying agents or any other ingredient usually used in the cosmetic and / or dermatological field.

The fatty substances may consist of an oil or a wax or mixtures thereof. By oil is meant a liquid compound at room temperature. By wax is meant a compound which is solid or substantially solid at ambient temperature and whose melting point is generally greater than 35 C.

As oils, mention may be made of mineral oils (paraffin); vegetable (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); such as perhydrosqualene, alcohols, acids or fatty esters (such as the C12-C15 alcohol benzoate sold under the trade name Finsolv TN by WITCO, octyl palmitate, isopropyl lanolate, triglycerides including those of capric / caprylic acids), oxyethylenated or oxypropylene fatty esters and ethers; silicone oils (cyclomethicone, polydimethylsiloxane or PDMS) or fluorinated oils, polyalkylenes.

Waxy compounds that may be mentioned include paraffin wax, carnauba wax, beeswax and hydrogenated castor oil.

Among the organic solvents, mention may be made of lower alcohols and polyols. These can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

The thickeners may be chosen in particular from crosslinked acrylic polymers such as Carbomer, crosslinked acrylate / C10-C30alkylacrylate polymers of the Pemulen type or polyacrylate-3 sold under the name VISCOPHOBE DB 1000 by Amerchol; polyacrylamides such as polyacrylamide emulsion, C13-C14 isoparraffine and laureth-7 sold under the name SEPIGEL 305 by SEPPIC, homopolymers or copolymers of AMPS such as HOSTACERIN AMPS sold by CLARIANT, guar gums and modified celluloses or non such as hydroxypropyl guar gum, methylhydroxyethylcellulose and hydroxypropylmethylcellulose, xanthan gum, nanoscale silica of the Aerosil type.

Of course, one skilled in the art will take care to choose the optional additional compound (s) mentioned above and / or their amounts in such a way that the advantageous properties intrinsically attached compositions in accordance with the invention are not, or substantially not , altered by the addition or additions envisaged.

The compositions according to the invention can be prepared according to the techniques well known to those skilled in the art, in particular those intended for the preparation of oil-in-water or water-in-oil type emulsions.

This composition may be in particular in the form of an emulsion, simple or complex (O / W, W / O, O / W / H or W / O / W) such as a cream, a milk, or in the form a gel or a cream gel, in the form of a lotion, an oil, a powder, a solid stick and optionally be packaged in an aerosol and be in the form of a mousse or a spray.

Preferably, the compositions according to the invention are in the form of an oil-in-water or water-in-oil emulsion.

<Desc / Clms Page number 15>

In the case of an emulsion, the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins, J. Mol Biol 13, 238 (1965)). FR 2 315 991 and FR 2 416 008).

When the cosmetic composition according to the invention is used for the care of the human epidermis, it may be in the form of a suspension or dispersion in solvents or fatty substances, in the form of a nonionic vesicular dispersion or in the form of a emulsion, preferably of the oil-in-water type, such as a cream or a milk, in the form of an ointment, a gel, a cream gel, a solar oil, a solid stick, a powder, an aerosol foam or of spray.

When the cosmetic composition according to the invention is used for hair care, it may be in the form of a shampoo, a lotion, a gel, an emulsion or a nonionic vesicle dispersion and may constitute, for example, a composition for rinsing, before or after shampooing, before or after coloring or bleaching, before, during or after permanent or straightening, a styling or treatment lotion or gel, a lotion or a gel for blow-drying or setting, a composition of perm or straightening, coloring or discoloration of hair.

When the composition is used as a makeup product for nails, lips, eyelashes, eyebrows or skin, such as epidermis treatment cream, foundation, lipstick stick, eye shadow, makeup with cheeks, mascara or liner also called "eyeliner", it can be in solid or pasty, anhydrous or aqueous, such as oil in water or water in oil emulsions, nonionic vesicular dispersions or suspensions.

As an indication, for the antisolar formulations in accordance with the invention which have an oil-in-water emulsion type support, the aqueous phase (including in particular the hydrophilic filters) generally represents from 50 to 95% by weight, preferably from 70 to 70% by weight. at 90% by weight, relative to the overall formulation, the oily phase (including in particular the lipophilic filters) of 5 to 50% by weight, preferably 10 to 30% by weight, relative to the whole of the formulation, and the or (co) emulsifier (s) from 0.5 to 20% by weight, preferably from 2 to 10% by weight, relative to the entire formulation.

As indicated at the beginning of the description, an object of the invention is the use of a composition as defined above for the manufacture of a cosmetic or dermatological composition intended for the protection of the skin and / or the hair against radiation ultraviolet, especially solar radiation.

Another object of the present invention resides in a process for improving the stability of at least one dibenzoylmethane derivative with respect to UV radiation by associating with said dibenzoylmethane derivative an effective amount of at least one derivative of 3 - (2-azacycloalkylidene) -1,3-dihydro-indol-2-one as defined above.

Another subject of the present invention consists in the use of a 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative as defined above in the preparation of a cosmetic or dermatological composition comprising at least one UV filter of the dibenzoylmethane derived type for the purpose of improving the UV stability of said dibenzoylmethane derivative.

Concrete but non-limiting examples illustrating the invention will now be given.

<Desc / Clms Page number 16>

Ce composé peut être acheté chez Specs/Biospecs sous la référence AH-262/33341016 ou être obtenu selon le procédé de synthèse défini ci-dessus à partir de 1-Ethyl-1,3dihydro-indol-2-one (cas : 61-28-9) et de 1-Méthyl-pyrrolidin-2-one (cas : 872-50-4). EXAMPLES EXAMPLE 1 In this example, the photostability of 4- (terbutyl) -4'-methoxydibenzoylmethane (solar filter "PARSOL 1789" from HOFFMANN LA ROCHE) was studied in the presence of a light-stabilizing compound according to the invention, namely: 1-Ethyl-3- (1-methyl-pyrrolidin-2-ylidene) -1,3-dihydro-indol-2-one (Compound 1)

This compound can be purchased from Specs / Biospecs under the reference AH-262/33341016 or be obtained according to the synthesis method defined above from 1-ethyl-1,3-dihydro-indol-2-one (case: 61- 28-9) and 1-methyl-pyrrolidin-2-one (case: 872-50-4).

By way of comparison, the photostability of this same filter was studied in the absence of this light stabilizing compound.

A solution at 0.2% (mass percentage) of Parsol 1789 and 0.8% of 1-ethyl-3- (1-methyl-pyrrolidin-2-ylidene) -1,3-dihydro-indol-2 was prepared. one (compound 1) in a mixture containing 20% Finsolv TN + 80% ethanol.

After evaporation, on a support, ethanol contained in 10 l of the solution described above, an oily film of average thickness -20 m containing 1% of Parsol 1789 + 4% of light-stabilizing compound is obtained. This film is exposed for one hour to the solar simulator (19 mW / cm 2 in UVA and 1.2 mW / cm 2 in UVB).

The compositions of these two formulas (FO-F1) were thus as follows (% by weight relative to the total weight of the formula):

<Tb>
<tb> Composition <SEP> Compound <SEP> light stabilizer <SEP> Support
<tb> FO <SEP> 0 <SEP>% <SEP> Common <SEP> Support *
<tb> (comparative)
<tb> F1 <SEP> 4 <SEP>% <SEP> Common <SEP> Support *
<tb> (invention)
<Tb>
* the composition of the common support was itself the following (% by weight relative to the total weight of the formula): - 4-tert-butyl-4'-methoxy-dibenzoylmethane (PARSOL 1789) 1% - C12-C15 alkyl benzoate (Finsolv TN) qs 100%

<Desc / Clms Page number 17>

 The photostability of Parsol 1789 in these formulations was quantified by HPLC assay of the residual filter.

The residual filter rate after irradiation is expressed mathematically by the ratio between the filter concentration measured in the irradiated sample and the initial concentration of this filter in the sample before irradiation.

The results obtained were as follows:
PARSOL 1789 residual
Compositions After 1 hour of irradiation
FO (comparative) 61%
F1 (Invention) 99% These results clearly demonstrate the remarkable photostabilization effect provided by 1-Ethyl-3- (1-methyl-pyrrolidin-2-ylidene) -1,3-dihydro-indol-2-one (compound 1) according to the invention on 4- (terbutyl) -4'-methoxy-dibenzoylmethane.

Ce composé peut être acheté chez Specs/Biospecs sous la référence AH-262/33341015 ou être obtenu selon le procédé de synthèse défini ci-dessus à partir de 1-Ethyl-1,3dihydro-indol-2-one (cas : 61-28-9) et de 1-Pyrrolidin-2-one (cas : 616-45-5). EXAMPLE 2 1-Ethyl-3-pyrrolidin-2-ylidene-1,3-dihydro-indol-2-one (Compound 2)

This compound can be purchased from Specs / Biospecs under the reference AH-262/33341015 or be obtained according to the synthesis method defined above from 1-ethyl-1,3-dihydro-indol-2-one (case: 61- 28-9) and 1-pyrrolidin-2-one (case: 616-45-5).

Ce composé peut être acheté chez Specs/Biospecs sous la référence AH-262/33341017 ou être obtenu selon le procédé de synthèse défini ci-dessus à partir de 1,3-Dihydroindol-2-one (cas : 59-48-3) et de 1-Pyrrolidin-2-one (cas : 616-45-5). On obtient un effet photostabilisant sur le 4-(terbutyl)-4'-méthoxy-dibenzoylméthane comparable à celui de l'exemple 1A light-stabilizing effect is obtained on 4- (terbutyl) -4'-methoxy-dibenzoylmethane comparable to that of Example 1. EXAMPLE 3 3-Pyrrolidin-2-ylidene-1,3-dihydro-indol-2-one (compound 3)

This compound can be purchased from Specs / Biospecs under the reference AH-262/33341017 or be obtained according to the synthesis method defined above from 1,3-Dihydroindol-2-one (case: 59-48-3). and 1-pyrrolidin-2-one (case: 616-45-5). A light stabilizing effect is obtained on 4- (terbutyl) -4'-methoxy-dibenzoylmethane comparable to that of Example 1

Claims (24)

 1. Cosmetic or dermatological composition, for topical use, characterized in that it comprises at least, in a cosmetically acceptable support: (a) at least one UV filter of the dibenzoylmethane type and (b) an effective amount of a 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative. 2. Composition according to claim 1, wherein the 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative has the following formula (I):

 in which: R1 and R3 are the same or different and may be: - a hydrogen atom, - a linear or branched, saturated or unsaturated C1-C22 alkyl group, optionally substituted by one or more groups Ai, - a ring of 4 to 7 atoms, saturated or unsaturated, optionally containing at least one heteroatom from N, O and S, optionally attached to another ring, optionally substituted by one or more groups Ai, these rings possibly comprising one or more carbonyl or thiocarbonyl functions, one of the groups C (= NR5) R'5, C (= NR5) NR'5R "5, COR5, CSR5, COORS, CONR5R'5, CSNR5R'5, SO2R5, SO2NR5R'5 with R5, R'5 and R "5 identical or different designating hydrogen, a linear or branched C 1 -C 22 alkyl radical or a ring of 4 to 7 atoms, which may contain at least one heteroatom from N, O, S, isolated or attached to another cycle, these cycles possibly comprising one or more carbonyl or thiocarbonyl functions, the alkyl radical or said cycles being saturated or not and optionally substituted by at least one substituent A2. R 2 and R 4 are identical or different and can be: a hydrogen atom, a linear or branched, saturated or unsaturated C 1 -C 22 alkyl group optionally substituted by one or more groups A1, a ring of 4 to 7 atoms, saturated or unsaturated, optionally containing at least one heteroatom from N, O and S, optionally substituted by one or more A1 groups, this ring being able to join to another ring or to the rings of the structure 3- (2-azacycloalkylidene) -1,3- dihydro-indol-2-one object of the invention, these rings may include one or more functions carbonyl or thiocarbonyl, this ring may also be positively charged as imidazolium, pyridinium, pyrazolium, triazolium, a halogen as F, CI, Br one of the groups CF3, CN, OR5, SR5, NR5R'5, C (= NR5) R'5, C (= NR5) NR'5R "5, NR5C (= NR'5) NR" 5R "5 , COR5, CSR5, COOR5, CONR5R'5, NR5COR'5, NR5CONR'5R "5, CSNR5R'5, SO2NR5R'5, NR5SO2R'5, SO2R5, NR5R'5R''5R '' '5+ with R5, R5 '5, R "5 and R' '' 5 identiq ues or different denoting hydrogen, a linear or branched C 1 -C 22 alkyl radical or a ring of 4 to 7 atoms, which may contain at least one heteroatom from N, O, S, isolated or attached to another ring, these cycles that may include one or more <Desc / Clms Page number 19>  NR5C (= NR'5) NR "5R" '5, CORS, CSR5, COORs, CONRsR's, NRsCOR's, NRSCONR'SR "5, CSNRsR's, SO2NR5R'5, NR5SO2R'5, SO2R5, SiR5R'5R" 5, SiRS ( Embedded image wherein R 5, R '5, R "5 and R'" 5 are the same or different and denote hydrogen, a linear or branched C1-C22 alkyl radical or a ring of 4 to 7 atoms, which may contain at least one heteroatom from N, O, S, isolated or attached to another ring, these rings possibly comprising one or more carbonyl functions; or thiocarbonyl, the alkyl radical or said rings being saturated or not and optionally substituted with at least one substituent A2 - a ring of 4 to 7 atoms, saturated or unsaturated, optionally containing at least one heteroatom from N, O and S, optionally substituted by one or more groups A2, this cycle being able to join another cycle or the cycles of the 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one structure which is the subject of the invention, these cycles possibly comprising one or more many carbonyl or thiocarbonyl functions, this ring may also be positively charged as imidazolium, pyridinium, pyrazolium, triazolium, A2 may be: - a halogen such as F, Cl, Br, - a linear or branched C1-C22 alkyl group, saturated or unsaturated one of the groups CF3, CN, OR, SR, NRR ', C (= NR) R', C (= NR) NR'R ", NRC (= NR ') NR" R "', COR, CSR, COOR, CONRR ', NRCOR', NRCONR'R ", CSNRR ', SO2NRR', NRS02R ', SO2R, SiRR'R", SiR (OSiR'R "R"') OSiR'R "R" ', NRR'R "R" '+ with R, R', R "and R" 'identical or different designating hydrogen or a linear or branched C1-C22 alkyl radical. y is 1,2,3 or 4; x is 1 to 2n + 2.

 carbonyl or thiocarbonyl functions, the alkyl radical or said rings being saturated or not and optionally substituted with at least one substituent A2; A1 may be: - a halogen such as F, Cl, Br, - a linear or branched, saturated or unsaturated C1-C22 alkyl group, optionally substituted with one or more A2 groups, - one of the groups CF3, CN, OR5, SR5 , NR5R'5, C (= NR5) R'5, C (= NR5) NR'5R "5, 3. Composition according to claim 2, wherein the compound of formula (I) is chosen from those of formula (II) or (III) below:

<Desc / Clms Page number 20>  in which: R 1 and R 3, which are identical or different, denote hydrogen, a linear or branched, saturated or unsaturated C 1 -C 6 alkyl radical, the phenyl group or a COR 5 or SO 2 R 5 radical with R 5 denoting a C 1 -C 4 alkyl radical; This linear or branched, saturated or unsaturated, or phenyl group; R2 is hydrogen; a linear or branched, saturated or unsaturated C 1 -C 6 alkyl radical; phenyl group; one of the radicals OR5, NR5R'5, NR5COR'5, COOR5 and CONRsR's with R5 and R'5, which may be identical or different, denoting hydrogen, a linear or branched, saturated or unsaturated C 1 -C 6 alkyl radical, or the group phenyl; the radical C F3; R4 denotes hydrogen, a linear or branched, saturated or unsaturated C 1 -C 6 alkyl radical, phenyl group or a radical OR 5 with R 5 denoting hydrogen, a linear or branched C 1 -C 6 alkyl radical, saturated or unsaturated , or the phenyl group; x, y and z are 1,2, 3 or 4. 4. Composition according to claim 3, wherein the compounds of formula (II) are chosen from those for which: R2 denotes hydrogen, OR5, NRsCOR's or NR5R'5 with R5 and R'5, which are identical or different, denoting the hydrogen, a linear or branched, saturated or unsaturated C 1 -C 6 alkyl radical, or the phenyl group; R4 is hydrogen; R 1 and R 3, which are identical or different, denote hydrogen, a linear or branched, saturated or unsaturated C 1 -C 8 alkyl radical or the phenyl group. 5. Composition according to claim 4, wherein the compounds of formula (II) are chosen from the following compounds:

 1-Ethyl-3- (1-methyl-pyrrolidin-2-ylidene) -1,3-dihydroindol-2-one 1-ethyl-3-pyrrolidin-2-ylidene-1,3-dihydroindol-2 pyrrolidin-2-ylidene-1,3-dihydro-indol-2-one. 6. Composition according to any one of claims 1 to 5, characterized in that the compound of formula (I) is present in the composition at a content ranging from 0.01 to 20% by weight, relative to the total weight. of the composition, preferably ranging from 0.1% to 10% by weight, relative to the total weight of the composition. 7. Composition according to any one of claims 1 to 6, characterized in that the dibenzoylmethane derivative is chosen from: - 2-methyldibenzoylmethane - 4-methyldibenzoylmethane - 4-isopropyldibenzoylmethane - 4-tert.-butyldibenzoylmethane 2,4-dimethyldibenzoylmethane - 2,5-dimethyldibenzoylmethane - 4,4'-diisopropyldibenzoylmethane - 4,4'-dimethoxydibenzoylmethane - 4-tert-butyl-4'-methoxydibenzoylmethane - 2-methyl-5 isopropyl-4'-methoxydibenzoylmethane - 2-methyl-5-tert.-butyl-4'-methoxydibenzoylmethane - 2,4-dimethyl-4'-methoxydibenzoylmethane - 2,6-dimethyl-4-tert-butyl -4'-methoxydibenzoylmethane. 8. Composition according to Claim 7, characterized in that the dibenzoylmethane derivative is 4- (terbutyl) -4'-methoxy-dibenzoylmethane. <Desc / Clms Page number 21> 9. Composition according to Claim 7, characterized in that the dibenzoylmethane derivative is 4-isopropyl-dibenzoylmethane. 10. Composition according to any one of claims 1 to 9, wherein the derivative of dibenzoylmethane is present in the composition at a content ranging from 0.01 to 20% by weight, relative to the total weight of the composition, preferably ranging from 0.1% to 10% by weight, relative to the total weight of the composition. 11. Composition according to any one of claims 1 to 10, wherein the cosmetically acceptable carrier is in the form of a type of emulsion oil-water or water-in-oil. 12. Composition according to any one of claims 1 to 11, characterized in that it further comprises one or more complementary organic or inorganic filters active in the UV-A and / or UV-B. 13. The composition of claim 12 characterized in that said complementary organic filters are selected from anthranilates; cinnamic derivatives, dibenzoylmethane derivatives; salicylic derivatives, camphor derivatives; triazine derivatives; benzophenone derivatives; ss, ssdiphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives; p-aminobenzoic acid derivatives (PABA); methylene bis (hydroxyphenyl benzotriazole) derivatives; filter polymers and silicone filters; dimers derived from alkylstyrene; 4,4-diarylbutadienes and mixtures thereof. 14. Composition according to Claim 13, characterized in that the said complementary organic screening agents are chosen from ethylhexyl salicylate, ethylhexyl methoxycinnamate octocrylene, phenylbenzimidazole sulphonic acid, benzophenone-3, benzophenone-4, benzophenone-5, 2- (4-diethylamino), and 2-hydroxybenzoyl) -benzoate benzoate. 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetra-sulfonate, 2,4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine Anisotriazine, Ethylhexyl triazone, Diethylhexyl Butamido Triazone, Methylene bis- Benzotriazolyl Tetramethylbutylphenol Drometrizole Trisiloxane 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene and mixtures thereof. 15. Composition according to claim 12, characterized in that the inorganic complementary filters are pigments or nanopigments of metal oxides, coated or not. <Desc / Clms Page number 22> 16. The composition as claimed in claim 15, characterized in that said pigments or nanopigments are chosen from titanium, zinc, iron, zirconium and cerium oxides and their mixtures, coated or otherwise. 17. Composition according to any one of claims 1 to 16, characterized in that it further comprises at least one agent for tanning and / or artificial browning of the skin. 18. Composition according to any one of claims 1 to 17, characterized in that it further comprises at least one adjuvant chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, humectants. , antioxidants, moisturizers, desquamants, antiradical agents, antipollution agents, antibacterials, anti-inflammatory agents, depigmenting agents, pro-pigmentants, opacifiers, stabilizers, emollients, silicones, anti-inflammatory agents foam, insect repellents, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, substance P antagonists, CGRP antagonists, fillers, pigments, polymers , propellants, alkalizing agents or acidifying agents 19. Composition according to any one of claims 1 to 18, characterized in that it is a protective composition of the human epidermis or an antisolar composition and that it is in the form of a non-ionic vesicle dispersion, an emulsion, in particular an oil-in-water emulsion, a cream, a milk, a gel, a cream gel, a suspension , a dispersion, an oil, a powder, a solid stick, a foam or a spray. 20. Composition according to any one of claims 1 to 18, characterized in that it is a makeup composition of the eyelashes, eyebrows, nails or skin and that it is in form solid or pasty, anhydrous or aqueous, an emulsion, a suspension or a dispersion. 21. Composition according to any one of claims 1 to 18, characterized in that it is a composition for protecting the hair against ultraviolet rays and is in the form of a shampoo, lotion, gel, emulsion, non-ionic vesicular dispersion. 22. Use of a composition as defined in claims 1 to 21 for the manufacture of cosmetic or dermatological compositions for the protection of the skin and / or hair against ultraviolet radiation, in particular solar radiation. 23. Process for improving the stability of at least one dibenzoylmethane derivative with respect to UV radiation, characterized in that it consists in associating with said dibenzoylmethane derivative an effective amount of 3- (2-azacycloalkylidene) derivative. 1,3-dihydro-indol-2-one as defined in any one of the preceding claims. 24. Use of a 3- (2-azacycloalkylidene) -1,3-dihydro-indol-2-one derivative as defined in any one of the preceding claims in the preparation of a cosmetic or dermatological composition comprising at least one minus a UV filter of the dibenzoylmethane derivative type for the purpose of improving the stability with respect to the UV rays of said dibenzoylmethane derivative.